N,n{40 -bis-{8 (1{40 -formamido-2{40 ,2{40 ,2{40 -trichloro)-ethyl{9 -imidazolidines

ABSTRACT

Compounds of the formula   AND Y is   WHEREIN X is -(CH2)2-, -(CH2)3- or   OR, WHEN X is -(CH2)3-, also -(CH2)2-;   AND Y is   OR, WHEN X is -(CH2)3-, also -(CH2)2-; where Z is hydrogen, phenyl, chlorophenyl, 2-furyl or 2-pyridyl; and A is tetramethylene or pentamethylene, each optionally having from 1 to 3 (alkyl of 1 to 4 carbon atoms)-substituents attached thereto, THE COMPOUNDS ARE USEFUL AS AGRICULTURAL FUNGICIDES.

White States atent 1 0st et al.

[ 51 Mar. 27, 1973 [54] N,N-BIS-[(l-FORMAMIDO-2,2,2'-

TR1CHLORO)-ETHYL]- IMIDAZOLIDINES [75] Inventors: Walter 0st; Klaus Thomas, both of Ingelheim am Rhein, Germany [73] Assignee: C. H. Boehringer Sohn, lngelheim am Rhein, Germany [22] Filed: Apr. 19, 1971 [21] Appl. No.: 135,415

[30] Foreign Application Priority Data Apr. 24, 1970 Germany ..P 20 19 844.1

[52] 11.8. Cl....260/309.7, 260/239 BF, 260/2564 Q,

260/2564 H, 260/295 AM, 260/561 R, 424/244, 424/251, 424/263, 424/273 51 Int. Cl. ..C07d 49/30 58 Field at Search ..260/309.7, 295 AM [56] References Cited FOREIGN PATENTS OR APPLICATIONS 408,938 9/1966 Switzerland ..260/309.7

OTHER PUBLICATIONS Bohme et al. Chem. Abst. Vol. 55, column 19778 (1961).QD1.A5I

Malz et al. Chem. Abst. Vol. 70, No. 3506a (1969). QDl.A5l

Ost et al. Chem. Abst. Vol. 74, No. l25726a (1971). QDLASI Primary Examiner-Natalie Trousof Attorney-Hammond & Littell 5 7 ABSTRACT Compounds of the formula wherein X is (CH (CHz)3 0F and Y is 3 Claims, No Drawings N,N'-BIS-[(1'-FORMAMIDO-2,2',2'-TRICHLOR0)- acetone, ethyl acetate and 1,1 ,2,2-tetrachloroethane, ETHYLl-IMIDAZOLIDINES as well as lower aliphatic alcohols, such as methanol or ethanol, or an aprotic solvent, such as dimethylformamide or dimethylsulfoxide. In those instances where an alkali metal carbonate is used as the acid acceptor, it is sometimes advantageous to provide as the solvent medium a mixture of water and an organic solvent which is water-immiscible or only sparsely water-miscible, such as ethyl acetate.

This invention relates to novel N,N'-bis-[(1-formamido-2',2,2'-trichloro)-ethyl]imidazolidines, hex- 5 ahydropyrimidines and homopiperazines, as well as to methods of preparing these compounds.

More particularly, the present invention relates to a novel class of imidazolidines, hexahydropyrimidines and homopiperazines of the formula 0 Method B ll By reacting an N,N-bis l-formamido-Z 2 2-tri- C-N -CHCC1 H H N a chloro)-ethyl]-alkylenediamine of the formula X Y HC-NHCHC c1; Hum-511% 01, 1:111 l 1) NH wherein X 18 --(CH,),--, (CH or lt l (JH-Cllz- 0 wherein X has the same meanings as in formula I, espeand Y is cially -(CH or --CH(CH )CH with an aldehyde of the formula on \(K\A OHC-Z (v 7. or when X is a|s0 wherein 2 has the same meanings as in formula I. The

reaction yields a compound of the formula I wherein Y is -CH(Z)-; it is carried out at a temperature of t0t80, fbl t t; tamethylene, each optically having from 1 to 3 (alabou o C pre era y a room tempera and y of 1 to 4 carbon atoms) substimems attached advantageously in the presence of a solvent, such as thereto mixtures of acetic acid and a lower aliphatic alcohol,

such as methanol.

The majority of the compounds of the formula I obtained by the above methods are crystalline substances; a few of them are amorphous. The basicity of the comwhere Z is hydrogen, phenyl, chlorophenyl, 2-furyl or 2-pyridyl; and A is tetramethylene or pen- The compounds embraced by formula I may be prepared by various methods involving known chemical principles, among which the following have proved to be particularly convenient and efficient:

pounds, except those where 2 IS pyridyl, 18 very low, so Method A that they form acid addition salts only with strong acids By reacting a l-formamido-2,2,2-trichloro-ethane under exclusion of moisture, and these salts are very derivative of the formula easily split by hydrolysis.

. e 6 The following examples further illustrate the present H invention and will enable others skilled in the art to un- HC NH (|JH CC1a derstand it more completely. It should be understood,

, (u) however, that the invention is not limited solely to the wherein R is a substituent easily removable as an pamcular examples gwen below anion, preferably chlorine or bromine, EXAMPLE 1 with an alicyclic diamine ofthe formula Y N,N'-Bis-[( l '-formamido-2',2',2'-trichloro)-ethyl]- imidazoline by method B 8 ml of a 30 percent formalin solution was added X Y dropwise to a suspension of 16.4 gm of N,N-bis-[(lformamido-2,2,2-trichloro)-ethyl]-ethylenediamine in (In) a mixture of 100 ml of tetrahydrofuran and 5 ml of aqueous. 50 percent acetic acid at room temperature, wherein X and Y have the same meanings aS in for while stirring the latter. A clear solution was formed 1. 50 after. a few minutes. The solution was stirred for 30 The reaction is advantageously performed in the minutes at room temperature, then the solvent was presence of an acid acceptor, preferably of a tertiary di illed off in vacuo, and the light-brown syrupy aliphatic amine, such as triethylamine, or of an alkali residue was dissolved in methanol. The resulting solumetal carbonate, such as sodium carbonate, at a tem tion was filtered, the filtrate was admixed with water perature between 10 and 100C, but preferab y at until it became turbid, and the turbid aqueous mixture room temperature, and optionally in the presence of a was cooled on ice. The crystalline precipitate formed inert solvent medium. Examples of suitable solvent thereby was collected by vacuum filtration, and the media for the reaction are tetrahydrofuran, dioxane, filter cake was washed with cold aqueous methanol and dried at 50C, yielding the compound of the formula having a decomposition point of 164-l 65C.

EXAMPLE 2 N,N'-Bis-[( l -formamido-2',2',2'-trichloro)-ethyl]-2- phenyl-imidazolidine by method B 8.1 gm of N,N'-bis-[(l-formamido-2,2,2-trichloro)- ethyl]-ethylenediamine were dissolved in a mixture consisting of 100 ml of methanol and 2.5 ml of aqueous 50 percent acetic acid; 2.1 gm of benzaldehyde were added to the solution, and the resulting mixture was allowed to stand at room temperature for 16 hours. Thereafter, the methanol was distilled off in vacuo, the viscous residue was dissolved in glacial acetic acid, and upon careful dropwise addition of water to the acid solution a crystalline precipitate formed. The crystals were collected by vacuum filtration and washed with ether, yielding the compound of the formula having a decomposition point of 2082l0C.

EXAMPLE 3 N,N '-Bis-[ l '-formamido-2',2',2'-trichloro)-ethyl]-2- (p-chloro-phenyl)-imidazolidine by method B A solution of6 gm of N,N'-bis-[( l-formamido-2,2,2- trichloro)-ethyl]-ethylenediamine and 8.5 gm of pchlorobenzaldebyde in 30 ml of glacial acetic acid was allowed to stand for three days at room temperature. Thereafter, about two-thirds of the acetic acid were distilled off in vacuo, and the residue was cooled, whereby a crystalline precipitate of colorless needles was formed; it was collected by vacuum filtration and washed with ether, yielding the compound of the formula having a decomposition point of 227C.

EXAMPLE4 N,N'-Bis-[(1'-formamido-2',2',2'-trichloro)ethyl]-2- (2"-furyl)-imidazolidine by method B A solution of 6 gm of N,N-bis-[( l-formamido-2,2,2 -trichloro)-ethyl]-ethylenediamine and 5 ml of 2-furaldehyde in 30 ml of glacial acetic acid was allowed to stand at room temperature for 48 hours. Thereafter, the acetic acid was distilled off in vacuo, the residue was admixed with ether, and the crystalline substance formed thereby was collected by vacuum filtration. The filter cake was identified to be the compound of the formula having a decomposition point of l 72C.

EXAMPLE 5 N,N'-Bis-[( l -formamido-2',2',2-trichloro)-ethyl]-2- (2"-pyridy|)-imidazolidine by method B A solution of6 gm ofN,N-bis-[( 1-formamido-2,2,2- trichloro)-ethyl]-ethylenediamine and 6.4 gm of pyridine-Z-aldehyde in 30 ml of glacial acetic acid was allowed to stand for 72 hours at room temperature. Thereafter, the acetic acid was distilled off in vacuo, the residual oil was dissolved in acetone, and the resulting solution was admixed with water until it became turbid, whereupon a crystalline substance separated out. The crystals were collected and recrystallized from dilute ethanol, yielding the compound of the formula having a decomposition point of 183C.

EXAMPLE 6 N,N -Bis-[( l '-formamido-2',2',2'-trichloro)-ethyl]- 2,Z-tetramethylene-imidazolidine by method A a. A solution of 12 gm of ethylenediamine in 30 ml of benzene was added dropwise over a period of three hours to a boiling solution of 16.8 gm of cyclopentanone in 200 ml of benzene, and the water formed by the reaction was continuously removed by means of a water separator. Thereafter, the benzene was distilled off in vacuo, and the residue was carefully fractionated in a high vacuum in an atmosphere of nitrogen. The fraction passing over between 107l08C at 0.6 mm Hg was 2,Z-tetramethylene-imidazolidine.

b. 3.7 gm of the 2,Z-tetramethylene-imidazolidine thus obtained and 6.0 gm of triethylamine were dissolved in 50 ml of tetrahydrofuran, and, while stirring the resulting solution, a solution of 12.4 gm of N- [(l,2,2,2-tetrachloro)ethyl]-formamide in 30 ml of tetrahydrofuran was added dropwise thereto. Thereafter, the reaction mixture was stirred for one hour more at room temperature, then the triethylamine hydrochloride which had formed was separated by vacuum filtration, and the filtrate was evaporated in vacuo. The semi-solid brown residue was repeatedly triturated with dry ether, whereby it solidified, yielding a slightly brownish solid substance having a decomposition point of l30-l 38C which was identified to be the solvate with 0.5 mol of ether of crystallization of the compound of the formula EXAMPLE 7 N,N'-Bis-[( l '-formamido-2',2',2'-trichloro)-ethyl]- 2,Z-pentamethylene-imidazolidine by method A a. Using a procedure analogous to that described in Example 6(a), 2,2-pentamethylene-imidazolidine, b.p.

53-54C at 0.06 mm Hg, was prepared from ethylenediamine and cyclohexanone.

b. Using a procedure analogous to that described in Example 6(b), 2,Z-pentamethylene-imidazolidine was reacted with N-[(l,2,2,2-tetrachloro)-ethyl]-formamide, and the amorphous raw product was crystallized from methylene chloride, yielding the compound of the formula having a decomposition point of l46147C.

EXAMPLE 8 N,N'-Bis-[( l '-formamido-2',2',2'-trichloro)-ethyl1- 2,2-( 3 "-methyl-pentamethylene)-imidazolidine method A a. Using a procedure analogous to that described in Example 6(a), 2,2-(3'-methyl-pentamethylene)- imidazolidine, b.p. 75-78C at 1 mm Hg, was prepared from ethylenediamine and 4-methyl-cyclohexanone.

b. Using a procedure analogous to that described in Example 6(b), 2,2-(3'-methyl-pentamethylene)- imidazolidine was reacted with N-[(l,2,2,2- tetrachloro)-ethyl]-formamide, yielding the compound of the formula having a melting point of 90-95C.

6 EXAMPLE 9 CH C (C1192 /CH2 CHz-C HCH: N

having a melting point of 981 02C.

EXAMPLE l0 N,N'-Bisl -formamido-2',2',2'-trichloro)-ethyl]- 2,2-( 3 '-tert.butyl-pentamethylene )-imidazolidine method A a. Using a procedure analogous to that described in Example 6(a), 2,2-(3'-tert.butyl-pentamethylene)- imidazolidine, b.p. 95-97C at 0.03 mm Hg, was prepared from ethylenediamine and 4-tert.butylcyclohexanone.

b. Using a procedure analogous to that described in Example 6(b), 2,2-(3'-tert.buty]-pentamethylene)- imidazolidine was reacted with N-[(l,2,2,2- tetrachloro)-ethyl]-formamide, yielding the compound of the formula having a melting point of 72-75C.

EXAMPLE ll N,N '-Bis-[( l '-formamido-2',-2',2-trichloro)-ethyl hexa-hydropyrimidine by method A A mixture consisting of 2.15 gm of hexahydropyrimidine (b.p. 5457C at 20 mm Hg), 5 gm of triethylamine and 75 ml of tetrahydrofuran was added dropwise to a solution of 10.5 gm of N-[( 1 ,2,2,2- tetrachloro)-ethyl]-formamide in 50 ml of tetrahydrofuran, and the resulting mixture was stirred for 30 minutes at room temperature. Thereafter, the precipitated triethylamine hydrochloride was separated by vacuum filtration, and the filtrate was evaporated in vacuo. The residual light-yellow oil crystallized upon digestion with n-hexane, yielding the solvate with 0.5

v precipitated mol of tetrahydrofuran of the compound of the formula having a melting point of 70C.

EXAMPLE 12 N,N'-Bis-[( 1 '-formamido-2',2,2'-trichloro)-ethyl]-2- methyl-hexahydropyrimidine Using a procedure analogous to that described in Example 11, 2-methyl-hexahydropyrimidine (b.p. 140-143C at 760 mm Hg) was reacted with N- [(1,2,2,2-tetrachloro)-ethyl]-formamide, yielding the compound of the formula initially as a viscous oil which gradually solidified upon standing in an exsiccator over P and then had a melting point of 63-65C.

EXAMPLE l3 N,N'-Bis-[( l '-formamido-2,2',2-trichloro)-ethyl]- homopiperazine Using a procedure analogous to that described in Example l 1, homopiperazine was reacted with N- [(1,2,2,2-tetrachloro)-ethyl]-formamide in ether in the presence of triethylamine. The reaction product together with the triethylamine hydrochloride and was separated from the latter by thorough washing first with water and then with ether, yielding the analytically pure compound of the formula having a decomposition point of 132135C.

EXAMPLE l4 N,N-Bis-[( l '-formamido-2',2,2'-trichloro)ethyl]-4- methyl-imidazolidine by method B 12 ml of an aqueous 30 percent formaldehyde solution were added dropwise to a solution of 21 gm of N,N'-bis-[( 1 '-formamido-2',2,2'-trichloro)-ethyl]- 1,2-propylenediamine in a mixture of 200 ml of methanol and 8 ml of aqueous 50 percent acetic acid, and the resulting mixture was allowed to stand for 30 minutes at room temperature. Thereafter, it was filtered, and the volatile components were distilled out of the filtrate in vacuo. The residue was dissolved in ethanol, and upon careful dropwise addition ofwater to the ethanolic solution a crystalline precipitate was formed. The precipitate was collected by vacuum filtration and thoroughly washed with n-hexane, yielding the compound of the formula i lib-NH-(FII-CCL:

having a decomposition point of 161-l62C.

EXAMPLE 15 N ,N-Bis-[( 1 -formamido-2,2,2-trichloro )-ethyl]-2- phenyl-4-methyl-imidazolidine 7 Using a procedure analogous to that described in Example 14, N,N'-bis-[( l -formamido-2',2,2-trichloro)- ethyll-l,2-propylenediamine was reacted with benzaldehyde, yielding the compound of the formula ll rrcavu-orr-o 013 l N W-onn 1130 .N

initially as a viscous oil which gradually solidified into the solvate with- 0.5 mol of methanol of crystallization having a melting point of 7274C.

EXAMPLE l6 having a melting point of 58-65C.

The compounds according to the present invention, that is, those embraced by formula I have useful properties. More particularly, they exhibit effective systemic fungitoxic activities against a multitude of phytopathogenic fungi with out damaging the plant s themselves. In other words, the compounds are absorbed by the plants and distributed throughout the plant system, whence they exert their fungitoxic activity. Thus the compounds are useful for combatting infestation of agricultural and ornamental plants by a large variety of phytopathogenic fungi; they may be applied by topical application, such as spraying or dusting, or by treating the soil in which the plants are growmg.

The compounds according to the present invention are especially effective against genuine mildew fungi on such cultivated plants as wheat, cucumbers, baneberry root, apple trees, gooseberries and ornamental plants; against rust fungi on wheat, beans and ornamental plants; against the cause of apple scab (Venturia inequalis); and against the cause of grey mildew, such as Botrytis cinerea.

Especially effective fungitoxics against genuine mildew fungi, either by topical or soil treatment, are the end products of Examples 1 and 7.

For use in combatting phytopathogenic fungi, the compounds of the present invention are compounded with conventional inert additives, such as solvents, dilu'ents, carriers, wetting agents, adhesion agents, emulsifiers and/or dispersants, optionally together with other biocidal agents, into conventional types of fungicidalcompositions, such as suspensions, emulsions, solutions, powders, granulates or aerosols. The effective fungitoxic concentration of the compounds according to the present invention in these compositions may range from 0.0001 to 90 percent by weight, based on the .total weight of the composition, depending upon the method of application and the desired degree of the fungitoxic effect. For instance, in sprayable liquid compositions, such as suspensions, emulsions, solutions and aerosols, the effective concentration may be as low as 0.0001 to 1 percent by weight, preferably 0.001 to 0.25 percent, depending upon the desiredfungitoxic effect, while in other compositions, such as powders, granulates and so-called low-volume-formulations, the concentration may be as high as 90 percent by weight.

The following examples illustrate a few fungitoxic compositions comprising a compound of the present invention as an active ingredient and represent the best modes contemplated of putting the invention into practical use. The parts are parts by weight unless otherwise specified. 1

EXAMPLE i7 Wettable powder The powder is compounded from the following ingredients:

Parts A compound of the formula 1 30 Kaolin 55 Lignin sulfonate 9 'Colloidal silicic acid Sodium tetrapropylene-benzene sulfonate 1 Total 100 The ingredients are intimately admixed with each other, and the mixture is ground into a powder. Prior to use, the powder is suspended in a sufficient'amount of water to make the concentration of the compound of the formula I in the suspension from 0.0001 to 0.25 percent by weight, depending upon the desired degree of fungitoxic effects. The aqueous suspension is a sprayable effective fungitoxic composition against genuine mildew fungi.

EXAMPLE l8 Aerosol .The aerosol composition is compounded from the followingingredients:

Parts A compound of the formula I 0.1 N-methyl-pyrrolidone l0.0 Sesame oil 0.1 Propellant (mixture of Frigens) 89.8 Total 100.0

The ingredients, other than the propellant, are admixed with each other, the mixture is charged into an aerosol container, and the container is pressurized with the propellant under pressure or deep refrigeration. The contents of the pressurized container, when discharged through a suitable aerosol valve, are an effective fungitoxic spray composition against genuine mildew fung1.

EXAMPLE l9 Emulsion concentrate The concentrate is compounded from the following ingredients:

Parts A compound of the formula l 15 Nonylphenol polyglycolether 20 l ,2Propyleneglycol l0 N-Methyl-pyrrolidone 55 Total I00 Ultra-low-volume concentrate The concentrate iscompounded from the following ingredients:

' Parts A compound of the formula I 20 Triethyleneglycol 38 N-Methyl-pyrrolidone 42 Total 100 The ingredients are intimately admixed with each other, and the resulting mixture is an effective fungitoxic ultra-low-volume spray composition against genuine mildew fungi.

EXAMPLE 21 Seed disinfectant powder The powder is compounded from the following ingredients:

Parts A compound of the formula I Kaolin 8 Sodium diisobutyl-naphthalene sulfonate 2 Total The ingredients are intimately admixed with each other, and the mixture is ground into a powder, which is an effective fungitoxic seed disinfectant against genuine mildew fungi.

The same results are obtained with a powder com-' pounded in like manner from the following ingredients:

Parts A compound of the formula I 75 Phenylmercury-pyrocatechol 5 Dyestuffs 3 Kaolin 14 Sodium diisobutyl-naphthalene sulfonate 3 Total 100 While the present invention has been illustrated with the aid of certain specific embodiments thereof, it' will be readily apparent to others skilled in the art that the invention is not limited to these particular embodiments, and that various changes and modifications may be made without departing from the spirit of the invention or the scope of the appended claims.

We claim:

1. A compound of the formula wherein X is (CH,), or

" f iir ir M CH:

and Y is CH, pa V 

2. A compound according to claim 1, which is N,N''-bis-((1''-formamido-2'',2'',2''-trichloro)-ethyl)-imidazolidine.
 3. A compound according to claim 1, which is N,N''-bis-((1''-formamido-2'',2'',2''-trichloro)-ethyl)-2,2-pentamethylene -imidazolidine. 